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  • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
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  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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  • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
  • B01J2231/12—Olefin polymerisation or copolymerisation
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  • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
  • B01J2231/12—Olefin polymerisation or copolymerisation
  • B01J2231/122—Cationic (co)polymerisation, e.g. single-site or Ziegler-Natta type
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  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
  • B01J2523/40—Constitutive chemical elements of heterogeneous catalysts of Group IV (IVA or IVB) of the Periodic Table
  • B01J2523/47—Titanium
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  • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
  • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B

Definitions

• Polymers have for a long time been desirable substances in the chemical industry.
• Polyethene and its derivatives, including co-polymers comprising ethene as one of the co-monomers are of particular commercial interest.
• One route for the preparation of polymers is by catalysed polymerisation of alkenes. The demand still remains in the state of the art for improved processes for the preparation of polymers from alkenes, especially for processes with long catalyst lifetimes, high specificity, and short induction times.
• a catalyst composition comprises: a titanate of the formula Ti(OR) 4 wherein each R is the same or different, and is a hydrocarbon residue; an ether catalyst modifier, preferably tetrahydrofuran, and an aluminoxane wherein the aluminoxane is a methyl aluminoxane, a modified methyl aluminoxane, or a combination comprising at least one of the foregoing.
• a process for the preparation of a downstream polymer product comprising contacting an alkene with the catalyst composition according to any of the preceding claims under conditions effective to form a polymer.
• FIG. 1 represents a schematic process for producing polymer product in accordance with one example of the presently disclosed subject matter.
• FIG. 2 represents a schematic process for producing polymer product in accordance with one example of the presently disclosed subject matter.
• the present invention is generally based on the object of overcoming at least one of the problems encountered in the state of the art in relation to the polymerisation reaction of an alkene, preferably an a-olefin, more preferably ethene, to give a polymer or downstream products derived therefrom.
• the present invention is further based on the object of providing a catalyst system and a process for a reaction which has a high product specificity, short induction time and a high catalyst lifetime.
• Another object is to provide an efficient and sustainable polymer source for producing downstream products and shaped bodies.
• a contribution to achieving at least one of the above-mentioned objects is made by a catalyst composition comprising the following catalyst components:
• a titanate with the general formula Ti(OR) 4 , wherein R is a hydrocarbon residue and each R can be the same as or different to the other R in the molecule;
• c. at least one or more selected from methyl aluminoxane and modified methyl aluminoxane.
• constituent c. is modified methyl aluminoxane.
• the modified aluminoxane is a copolymer comprising (MeAlO) as a first repeating unit and (RAIO) as a further repeating unit, wherein R is not methyl.
• the ratio between the number of first repeating units and the number of further repeating units is in the range from about 20: 1 to about 1: 1, preferably in the range from about 15: 1 to about 5: 1, more preferably in the range from about 12: 1 to about 8: 1.
• the catalyst composition comprises a further aluminium compound distinct from the methyl aluminoxane c.
• the further aluminium compound has the general formula Al n R3 n , wherein n is 1 or 2, R is a hydrocarbon residue, H or a halogen, preferably a hydrocarbon residue or a halogen, more preferably an alkyl group or aryl group or halogen, most preferably an alkyl group or a halogen.
• the further aluminium compound is selected from the group consisting of the following: A1H 3 , AlEth 3 Cl 3 and A1C1 3 .
• the molar ratio between the further aluminium compound and the total amount of methyl aluminoxane and modified aluminoxane is in the range from about 1:5 to about 5: 1, preferably in the range from about
• the catalyst is dissolved in a liquid.
• the liquid is an alkane or an alkene.
• the liquid is a C 6 -Ci 2 alkane or a C 6 -Ci2 alkene.
• the liquid is at least one or more selected from the group consisting of butene, hexane, heptane, and octane.
• the titanate is Ti(0-butyl) 4 .
• the titanate is Ti(0-n-alkyl) 4 .
• the titanate is Ti(0-n-butyl) 4 .
• the ether is tetrahydrofuran.
• a contribution to achieving at least one of the above mentioned objects is made by a process for the preparation of a polymer, wherein an alkene comes into contact with a catalyst composition according to the invention.
• the polymer is a poly ethene.
• the alkene and the catalyst composition come into contact in a homogeneous liquid phase.
• the pressure of the system is in the range from about 5 to about 50 bar;
• the temperature of the system is in the range from about 40 to about 80 °C.
• a contribution to achieving at least one of the above mentioned objects is made by a process for the preparation of a downstream product comprising the following preparation steps: i. preparation of a polymer according to the invention,
• the downstream product is converted into a shaped body.
• a contribution to achieving at least one of the aforementioned objects is made by a catalyst composition.
• Preferred catalyst compositions in the context of this invention catalyse the reaction of an alkene, preferably ethene, to obtain a polymer, preferably a polyethene. It is preferred that the catalyst composition contribute to favourable properties of the reaction, preferably to improved catalyst activity, product selectivity of the required polymer, an increased catalyst lifetime.
• a preferred catalyst composition comprises a titanate, preferably tetra-n-butyl titanate; an ether catalyst modifier, preferably tetrahydrofuran; one or more selected from the group consisting methyl aluminoxane, modified methyl aluminoxane, and a combination comprising at least one of the foregoing.
• the catalyst composition comprises a further aluminium compound distinct from c.
• Preferred titanates are compounds of the general formula Ti(OR) 4 , wherein R stands for a hydrocarbon residue, preferably an alkyl group or an aryl group, more preferably an alkyl group, and each R in a molecule may be the same as or different to the other R groups in the molecule. Titanates are known to the skilled person, and the specific titanate may be selected in order to enhance the advantageous properties of the process.
• R is preferably a straight chain or branched alkyl group, more preferably straight chain.
• R is preferably a C 2 -C 12 alkyl group, more preferably a C 2 -C8 alkyl group, most preferably a C 3 - C5 alkyl group.
• the preferred alkyl group is butyl, which includes n-butyl and iso-butyl.
• Suitable organic titanium compounds include, but are not limited to, tetraethyl titanate, tetraisopropyl titanate, titanium tetra-n-butoxide (TNBT), and tetra-2-ethylhexyl titanate.
• the organic titanium compound is titanium tetra-n-butoxide.
• the titanate can be present in high concentration in the reaction mixture, for example in a concentration of about 0.0001 to about 0.1 mol/dm , about 0.0002 to about 0.01 mol/dm 3 , more preferably about 0.0005 to about 0.001 mol/dm 3 .
• aluminoxane to act as catalyst activator.
• the skilled person has knowledge of methyl aluminoxanes and he may select any methyl aluminoxane and/or modified methyl aluminoxane which he considers suitable for increasing favourable properties of the invention.
• Preferred methyl aluminoxanes are compounds with the general formula (CH 3 A10) n .
• Preferred modified methyl aluminoxanes are compounds with the general formula (R a (CH 3 ) b A10) n wherein a in the range from 0 to 1 and b is equal to 1-a, and wherein R is not methyl.
• R groups in this context are alkyl groups, preferably C 2 -C 10 alkyl groups, more preferably octyl or butyl, most preferably butyl. It is preferred for a to be in the range from about 0.01 to about 0.5, more preferably in the range from about 0.02 to about 0.4, most preferably in the range from about 0.03 to about 0.35.
• the further organic aluminum compound is a compound of the formula A1R 3 , wherein R stands for a hydrocarbon, hydrogen or a halogen, preferably a hydrocarbon or a halogen, more preferably alkyl or aryl or halogen, most preferably an alkyl group or halogen and each R in a molecule may be the same as or different to the other R groups in the molecule.
• Aluminium compounds are known to the skilled person, wherein specific aluminium compounds are selected in order to enhance the advantageous properties of the process.
• R is preferably a straight chain or branched alkyl group, more preferably straight chain.
• R is preferably a Ci-Ci 2 alkyl group, more preferably a Ci-C 8 alkyl group, most preferably a Ci-C 4 alkyl group.
• the preferred alkyl group is ethyl.
• Suitable organic aluminum compounds include, but are not limited to, triethylaluminum (TEAL), tripropylaluminum, triisobutylaluminum, diisobutylaluminum hydride, and trihexylaluminum. In some embodiments, the organic aluminum compound is triethylaluminum.
• the catalyst composition comprises a catalyst modifier, in particular an amine catalyst modifier or an ether catalyst modifier.
• a catalyst modifier in particular an amine catalyst modifier or an ether catalyst modifier.
• ether catalyst modifiers are known, and can act as a co-catalyst or catalyst modifiers to the titanate, preferably by coordination of the titanate with a lone pair of electrons.
• Such ether catalyst modifiers are well known to the skilled person and he may select any ether which he considers to be appropriate in the context and preferably improving the favourable characteristics of the reaction, preferably a reduced initiation time, increased yield and reduced polymer fouling.
• Preferred ether catalyst modifiers may be monoethers or polyethers.
• Preferred substituents of the ether are alkyl groups.
• Preferred alkyl groups are methyl, ethyl, propyl, n- butyl, iso-butyl, t-butyl, and other higher alkyl groups.
• Some preferred monoether catalyst modifiers are dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, methyl ethyl ether, methyl propyl ether, methyl butyl ether, ethyl propyl ether, ethyl butyl ether, propyl butyl ether, tetrahydrofuran, or dihydropyran.
• the preferred mono ether is tetrahydrofuran.
• Preferred polyether catalyst modifiers are 1,4 dioxane or ethers based on polyalcohols, preferably glycols or glycerols, preferably ethylene glycol.
• Preferred ethers based on glycol are dimethyl ethylene glycol, diethyl ethylene glycol, dipropyl ethylene glycol, dibutyl ethylene glycol, methyl ethyl ethylene glycol, methyl propyl ethylene glycol, methyl butyl ethylene glycol, ethyl propyl ethylene glycol, ethyl butyl ethylene glycol, propyl butyl ethylene glycol.
• an ether catalyst modifier is present, and tetrahydrofuran is preferred.
• the catalyst composition contains at least two or more ether catalyst modifiers, preferably with at least one or more, preferably all, as described above, preferably with one of the ethers being tetrahydrofuran.
• the catalyst composition may be present dissolved in a liquid, preferably an alkane, preferably hexane, preferably as a homogeneous liquid.
• the liquid is an alkane or an alkene or an aromatic solvent.
• the liquid is a C 4 -Ci 2 alkane, preferably a C 4 -C 8 , more preferably a C 4 -C 6 alkane; or a C 4 -Ci 2 alkene, preferably a C 4 -C 8 alkene, more preferably a C 4 -C 6 alkene.
• the liquid is one or more selected from the group consisting of butene, hexane, heptane, and octane.
• the catalyst composition may be pre -prepared or prepared in situ, and preferably is pre-prepared.
• the components of the catalyst composition are introduced to the reaction system as two or more components that are added sequentially.
• the titanate is pre-mixed with an ether catalyst modifier, optionally together with the catalyst additive.
• they are mixed in an inert solvent, preferably an alkane, preferably one or more of the following: pentane, hexane, heptane, octane, nonane, or decane, preferably hexane.
• the aluminoxane, and the optional organic aluminum compound are premixed, preferably in the absence of an olefin (alkene).
• they are mixed in an inert solvent, preferably an alkane, preferably one or more of pentane, hexane, heptane, octane, nonane, or decane, preferably hexane.
• the titanate, the ether catalyst modifier, aluminoxane, and the optional organic aluminium compound are premixed, preferably in the absence of olefin.
• they are mixed in an inert solvent, preferably an alkane, preferably one or more selected from the group consisting of the following: pentane, hexane, heptane, octane, nonane, decane, preferably hexane.
• the catalyst additive can further be optionally mixed at the same time with these components in the inert solvent.
• no more than 10% of alkene is present in the preparation of the catalyst compositions.
• no alkene is present in any of the steps of the catalyst preparation.
• the catalyst composition first comes into contact with alkene during the reaction for the preparation of the a-olefin.
• no polymer is present or created in the catalyst composition during its preparation.
• the catalyst composition is prepared shortly before use in the preparation of an a-olefin. It is preferred for the prepared catalyst system not be stored for longer than 1 week, preferably not longer than 1 day, more preferably not longer than 5 hours before being employed as catalyst for the preparation of an ⁇ -olefin or other reaction process.
• the catalyst composition is not activated until shortly before being employed in the reaction. It is preferred that the aluminoxane and the optional organic aluminium compound not be brought into contact with the other catalyst components earlier than 30 minutes, preferably not earlier than 15 minutes, more preferably not earlier than 10 minutes, most preferably not earlier than 5 minutes before the catalyst composition is employed in the reaction.
• the individual components it is preferred for the individual components to be prepared shortly before use. It is preferred that at least one or more of the catalyst components not be stored for longer than 1 week, preferably not longer than 1 day, more preferably not longer than 5 hours after its preparation and before being employed as a component of the catalyst for the reaction.
• the titanate is not stored for longer than 1 week, preferably not longer than 1 day, more preferably not longer than 5 hours after its preparation and before being employed as a component of the catalyst in the reaction.
• the organic aluminium compound is not stored for longer than 1 week, preferably not longer than 1 day, more preferably not longer than 5 hours after its preparation and before being employed as a component of the catalyst for the reaction.
• a contribution to achieving at least one of the above mentioned objects is made by a reaction process for the preparation of a polymer from an alkene, preferably a reaction process for preparation of a from a C 2 -C8 alkene, most preferably a process for preparation of polyethene from ethene.
• an alkene preferably a C 2 -C 8 alkene, most preferably ethene
• the polymer includes at least 2 repeat units based on the alkeneThe alkene and the catalyst may come into contact in a homogeneous liquid phase.
• Preferred polymerisation reactions can be mono-polymerization (i.e., homopolymerisation) reactions or copolymerization reactions, preferably copolymerization reactions.
• the preferred homopolymerisation product is polybutene.
• the preferred copolymers comprise units derived from the a-olefin, preferably 1-butene, and one or more co- monomers such as ethene, propene, pentene, styrene, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile, or vinyl chloride, preferably ethene.
• the preferred copolymer is a copolymer of ethene and 1-butene, preferably with a larger weight percent (wt.%) of units derived from ethene monomers than of units derived from 1-butene monomers, preferably with a weight ratio of ethene units to 1-butene units of about 50: 1 to about 5: 1, more preferably about 30: 1 to about 10: 1, most preferably about 25: 1 to about 15: 1.
• the skilled person may vary the ratio relating the mass of ethene monomers and 1-butene monomers in order to achieve the desired properties of the copolymers, such as crystallinity and elasticity.
• the reaction is carried out as a flow reaction. In other embodiments, the reaction is carried out as a batch reaction. It is preferred that the reaction proceed as a homogeneous liquid phase reaction.
• FIG. 1 shows a schematic process diagram 100 for an example batch process in accordance with the presently disclosed subject matter.
• the catalyst composition is prepared.
• the catalyst composition and olefin, e.g., ethylene are brought into contact in the liquid phase, e.g., in 1-butene as a solvent.
• the polymer product of the reaction e.g., polyethene
• the catalyst composition can be salvaged from the product mix. The catalyst composition can thus be recycled.
• FIG. 2 shows a schematic process diagram 200 for an example flow process in accordance with the presently disclosed subject matter.
• the catalyst composition is prepared and introduced into the reaction system, e.g., 1-butene solvent system.
• the catalyst composition components can either be premixed or added sequentially.
• the alkene e.g., ethylene
• the polymer product e.g., polyethene
• the skilled person can select the solvent for the reaction process in order to improve the advantageous properties of the reaction.
• the solvent for the reaction is preferably an alkane, an alkene, or an aromatic hydrocarbon.
• Preferred alkanes in this context are C2-C12 alkanes, preferably C 4 -C 8 alkanes, most preferably hexane, heptane, or octane, including all isomers of each, and more preferably n-hexane.
• Preferred alkenes in this context are C2-C12 alkenes, preferably C 4 -C 8 alkenes, including all isomers of each, most preferably butene.
• Preferred aromatic hydrocarbons in this context are benzene, toluene, and phenol.
• the solvent for the reaction is different than the solvent employed for preparation of the catalyst system.
• the reaction can be performed at a temperature of from about 20°C to about 150°C, from about 40°C to about 100°C, from about 20°C to about 70°C, from about 50°C to about 70°C, from about 50°C to about 55°C, or from about 55°C to about 65°C. In some embodiments, the reaction is performed at a temperature of about 60°C.
• the reaction can be performed at a pressure of from about 5 bars to about 50 bars, from about 10 bars to about 40 bars, or from about 15 bars to about 30 bars. In some embodiments, it is preferred that at least one of the following conditions be satisfied during the reaction:
• the pressure of the system is about 1 to about 50 bar, preferably about 5 to about 50 bar, more preferably about 10 to about 40 bar, most preferably in the range from about 15 to about 30 bar; or
• the temperature of the system is about 30 to about 150°C, preferably about 40 to about 100°C, more preferably about 50 to about 70°C, most preferably about 55 to about 65 °C.
• the reaction is conducted in a batch where a selected volume of the presently disclosed catalyst composition can be introduced into a reactor provided with usual stirring and cooling systems, and can be subjected therein to an ethylene pressure, which can be from about 22 bars to about 27 bars. In some embodiments, the reaction using the presently disclosed catalyst composition is conducted at an ethylene pressure of about 23 bars.
• ethylene pressure can be from about 22 bars to about 27 bars.
• the reaction using the presently disclosed catalyst composition is conducted at an ethylene pressure of about 23 bars.
• One of ordinary skill in the art can adjust the temperature, pressure and other conditions of the reaction in order to bring about favorable properties of the reaction, for example, in order to ensure that the reaction system is present as a homogeneous liquid phase.
• the solvent for the reaction is 1 -butene, in order to ensure that the reaction system is present as a homogeneous liquid phase.
• the skilled person may adjust the temperature, pressure and other conditions of the reaction in order to bring about favourable properties of the reaction and in order to ensure that the reaction system is present as a homogeneous liquid phase.
• the alkene and the catalyst come into contact in a liquid phase comprising at least 50 wt. % but-l-ene, based on the total weight of the liquid phase.
• reaction product may be extracted by any method which the skilled person considers to suitable in the context.
• Preferred methods of extraction include distillation, precipitation, crystallisation, membrane permeation, and the like.
• the polymers are further processed.
• this further processing preferably involves formation of shaped objects such as plastic parts for electronic devices, automobile parts, such as bumpers, dashboards, or other body parts, furniture, or other parts or merchandise, or for packaging, such as plastic bags, film, or containers.
• Polymer fouling was identified by visual inspection and by using a metal spatula to scrape the inside surfaces of the reactor following completion of the reaction.
• a thin layer of polymer can be seen on the surfaces of the walls of the reactor and/or on the stirrer.
• the thin polymer layer is white is colour and includes thin strands.
• Initiation time was determined by monitoring the pressure in the reactor or the flow rate of the feed to the reactor. Once the reaction starts, ethene feed is consumed.
• onset of reaction is manifested as a drop in absolute pressure.
• pressure remains roughly constant during the initiation period and starts to drop once the initiation period is over.
• the initiation time is the time spent at roughly constant pressure once the reactants and catalyst have been brought into contact and before the reaction starts.
• onset of reaction is manifest as an increase in the flow rate of ethene entering the reactor.
• Ethene flows into the reactor once the initiation period is over.
• the initiation time is the time spent at roughly zero flow rate once the reactants and catalyst have been brought into contact and before the reaction starts.
• Example 1 illustrates the catalyst system including a tetra-substituted titanate, a dibutyl ether, and trialkyl aluminium, and its use in a process for the preparation of an a- olefin from an alkene, in particular preparation of 1-butene from ethene.
• the results are summarized in Table 1.
• Example la The reaction is carried out in a batch reactor (Parr 300 ml Autoclave Model 4566 Mini Benchtop reactor) at 60 °C and 23 bar. This temperature and pressure ar maintained in the reactor throughout the reaction. 0.25 ml tetra-n-butyl titanate (Dorf KETAL) and 0.25 ml dibutyl ether (Aldrich) are introduced into 50 ml n-hexane (Aldrich). To this is added 1.8 ml 1M solution of triethyl aluminium in n-hexane. The catalyst system in hexane is introduced into the reactor. The reaction system is heated to 60 °C under stirring and pressured to 23 bar with ethene for 1 hour. The product is collected in an adjacent vessel after depressurising.
• Dorf KETAL 0.25 ml dibutyl ether
• Aldrich 1.8 ml 1M solution of triethyl aluminium in n-hexane.
• Example lb (comparative). Example la is repeated except with 0.25 ml tetrahydrofuran in place of 0.25 ml dibutyl ether.
• Example lc. Example la is repeated except with a mixture of 0.125 ml tetrahydrofuran and 0.125 ml dibutyl ether in place of 0.25 ml dibutyl ether.
• Example 2 illustrates the catalyst system comprising tetraalkyl titanate, a silicate, and trialkyl and its use in a process for the preparation of an a-olefin from an alkene, in particular preparation of 1-butene from ethene.
• the results are summarized in Table 2.
• Example 2a The reaction was carried out in a batch reactor (Parr 300 ml Autoclave Model 4566 Mini Benchtop reactor) at 60 °C and 23 bars. This temperature and pressure were maintained in the reactor throughout the reaction. 0.25 ml tetra-n-butyl titanate (Dorf KETAL) and 0.25 ml tetraethyl silicate (Aldrich) were introduced into 50 ml n-hexane (Aldrich). To this was added 1.8 ml 1M solution of triethyl aluminium in n-hexane. The catalyst system in hexane was introduced into the reactor.
• Dorf KETAL 0.25 ml tetraethyl silicate
• Aldrich 0.25 ml tetraethyl silicate
• the reaction system was heated to 60 °C under stirring and pressured to 23 bar with ethene for 1 hour.
• the product was collected in an adjacent vessel after depressurising.
• the yield of 1-butene, expressed as the percentage based on full conversion of the introduced ethene, was 90%. No polymer fouling was observed.
• Example 2b (comparative). Example 2a was repeated except with 9 ml tetrahydrofuran in place of 25 ml tetraethyl silicate. The observed yield was ⁇ 1%. Some polymer fouling was observed.
• Example 3 illustrates the catalyst system comprising a titanate, an ether, a methyl aluminoxane, and optionally a second aluminum compound, and its use in a process for the preparation of an polymer from an alkene, in particular preparation of polyethylene from ethene.
• Example 3a The reaction was carried out in a batch reactor (Parr 300 ml Autoclave Model 4566 Mini Benchtop reactor) at 60 °C and 23 bar. This temperature and pressure were maintained in the reactor throughout the reaction. 0.25 ml tetra-n-butyl titanate (Dorf KETAL) and 0.25 ml tetrahydrofuran (Aldrich) were introduced into 50 ml n-hexane (Aldrich). To this was added 1.8 ml 1M solution of methyl aluminoxane in n-heptane (MAO). The catalyst system in hexane was introduced into the reactor.
• Dorf KETAL 0.25 ml tetra-n-butyl titanate
• Aldrich 0.25 ml tetrahydrofuran
• the reaction system was heated to 60 °C under stirring and pressured to 23 bar with ethene for 1 hour.
• the product was collected in an adjacent vessel after depressurising.
• the yield of polymer expressed as the percentage based on full conversion of the introduced ethene, was 95%.
• Example 3b Example 3a was repeated except that 1.8 ml 1M solution of modified methyl aluminoxane (CH 3 )o.7(iso-But)o .3 (MMAO) was employed in place of the methyl aluminoxane.
• CH 3 modified methyl aluminoxane
• MMAO modified methyl aluminoxane
• Example 3c Example 3a was repeated except that a mixture of 0.9 ml 1M solution of methyl aluminoxane and 0.9 ml 1M triethyl aluminium (TEAL) was employed in place of the methyl aluminoxane.
• TEAL triethyl aluminium
• Example 3d Example 3a was repeated except that a mixture of 0.9 ml 1M solution of modified methyl aluminoxane (CH 3 )o.7(iso-But)o. 3 and 0.9 ml 1M triethyl aluminium was employed in place of the methyl aluminoxane.
• Example 3e (Comparative). Example 3a was repeated except that 1.8 ml 1M solution of triethyl aluminium was employed in place of the methyl aluminoxane.
• Embodiment 1 A catalyst composition, comprising: a titanate of the formula Ti(OR) 4 wherein each R is the same or different, and is a hydrocarbon residue; an ether catalyst modifier, preferably tetrahydrofuran; and an aluminoxane wherein the aluminoxane is a methyl aluminoxane, a modified methyl aluminoxane, or a combination comprising at least one of the foregoing.
• a titanate of the formula Ti(OR) 4 wherein each R is the same or different, and is a hydrocarbon residue
• an ether catalyst modifier preferably tetrahydrofuran
• an aluminoxane wherein the aluminoxane is a methyl aluminoxane, a modified methyl aluminoxane, or a combination comprising at least one of the foregoing.
• Embodiment 2 The catalyst composition of any one or more of the preceding embodiments, wherein the titanate is Ti(0-butyl) 4 , Ti(0-n-alkyl) 4 , Ti(0-n-butyl) 4i or a combination comprising at least one of the foregoing;
• Embodiment 3 The catalyst composition of any one or more of the preceding embodiments, wherein the modified methyl aluminoxane is a copolymer comprising MeAlO repeating units and R AlO repeating units wherein R is a C2-12 hydrocarbon, preferably wherein a ratio of the number of MeAlO repeating units and the number of R AlO repeating units is about 20: 1 to about 1: 1.
• Embodiment 4 The catalyst composition of any one or more of the preceding embodiments, comprising a further organic aluminium compound distinct from the methyl aluminoxane and from the modified methyl aluminoxane, preferably wherein a molar the ratio between the aluminoxane and the organic aluminium compound is about 1:5 to about 5: 1.
• Embodiment 5 The catalyst composition of embodiment 4, wherein the organic aluminium compound is of the formula Al n R3 n , wherein n is 1 or 2 and each R is the same or different, and is hydrogen, a hydrocarbon residue, or halogen, preferably wherein the aluminium compound is triethyl aluminium.
• Embodiment 6. A process for the preparation of a polymer, the process comprising contacting an alkene with the catalyst composition according to any of the preceding embodiments under conditions effective to form a polymer.
• Embodiment 7 The process according to embodiment 6, wherein the alkene is ethene and the polymer is polyethylene.
• Embodiment 8 The process according to embodiment 6 or 7, wherein the contacting is in a homogeneous liquid phase.
• Embodiment 9 The process according to any one or more of embodiments 6 to 8, wherein the conditions include at least one of a pressure of about 5 to about 50 bar, or a temperature of about 40 to about 80°C.
• Embodiment 10 The process according to embodiment any one or more of embodiments 6 to 9, further comprising shaping the polymer to provide an article.

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